The enantiomers of N,N’–bis(1–phenylethyl)–2,6–pyridinedicarboxamide (L), namely (R,R)–1, and (S,S)–1, react with Ln(III) ions to give stable [LnL3]3+ complexes in anhydrous acetonitrile solution and in the solid state, as evidenced by ES–MS, NMR and luminescence titrations, and their X–ray crystal structures, respectively. All [LnL3]3+ complexes (Ln(III) = Eu, Gd, Tb, Yb, and L = (R,R)–1, and (S,S)–1)) are isostructural and crystallize in the cubic space group I23. Although the small quantum yields of the Ln(III)–centered luminescence clearly point to the poor efficiency of the luminescence sensitization by the ligand and the intersystem crossing (ISC) and ligand–to–metal energy transfers, the ligand triplet–excited–state energy seems relatively well suited to sensitize many Ln(III) ion’s emission, for instance, in the VIS (Eu, Tb), NIR (Nd, Yb), or in both regions (Pr, Sm, Dy, Er, Tm).